Method of preparing phosphorous containing oligomers or polymers

ABSTRACT

Phosphorus-containing oligomers or polymers useful as flameresistant substances are obtained by reacting a tertiary phosphite (A) of the general formula:

United States Ptent n 1 Yoshizawa et a1.

[ Sept. 18, 1973 METHOD OF PREPARING PHOSPHOROUS CONTAINING OLIGOMERS ORPOLYMERS [73] Assignees: Dainippon Ink & Chemicals, Inc.,

Tokyo; The Dainippon Ink Institute of Chemical Research, Saitama Pref.,both of J apan [22] Filed: Aug. 21, 1970 [21] Appl. No.: 66,153

[30] Foreign Application Priority Data Aug. 25, 1969 Japan 44/6650][5'21 U.S. Cl 260/931, 117/137, 162/159,

260/45.7 P, 260/968, 260/969 [51] Int. Cl. C07f 9/40, D06c 27/00 [58]Field of Search 260/931, 968, 969

[56] References Cited UNITED STATES PATENTS 12/1961 Birum 260/931 X12/1961 Birum 260/931 3/1968 Chess et al 260/931 X PrimaryExaminer-Lewis Gotts Assistant Examiner-Anton H. Sutto Attorney-Oblon,Fisher and Spivak [57] ABSTRACT Phosphorus-containing oligomers orpolymers useful as flame-resistant substances are obtained by reacting atertiary phosphite (A) of the general formula:

( l M, (A)

a dialkyl phosphite halogenide (B) of the general formula:

(R O) PX, (B)

a cyclic halogenophosphite (C) of the general formula:

an aldehyde (D) of the general formula:

' R CHO (D) and a ketone (E) of the general formula:

wherein R to R and X are as defined below.

2 Claims, No Drawings METHOD OF PREPARING PHOSPHOROUS CONTAININGOLIGOMERS OR POLYMERS BACKGROUND OF THE INVENTION 1. Field Of TheInvention:

The present invention relates to a process for imparting lastingflame-resistant effects to various combustible materials.

2. Description Of The Prior Art:

Various substances have been proposed as flameresisting additives forcombustible materials, such as fibers and plastics. For example, variousorganic halogen compounds, phosphoric acid esters, halogencontainingphosphoric acid esters, antimony oxide and boric acid salts have beenused. Though those substances are effective in general, they aregenerally water-soluble, low in molecular weight and characterized byion exchange properties. Further they have the additional defect that ifthey are added to materials such as fibers and plastics, they can moveto the surface of the materials where they are lost or scattered as timeelapses, thus reducing or losing the flame-resistant properties. It isknown that a Proban treatment in which tetrakishydroxymethyl phosphoniumchloride is used, provides lasting flame-resisting effects due to itsreactivity with cellulose. However, that process cannot be applied tomaterials which do not have functional groups. Moreover, that processcauses hardening of finished fabrics or emittance of an offensive odorduring storage. When conventional low molecular weight flame-resistingagents are used, the physical properties such as tensile strength,flexal strength, abrasion resistance and weather resistance of thefibers of plastics are remarkably reduced, and the hand of woven clothis inclined to deteriorate remarkably. Further some of low molecularweight flame-resistant agents are poisonous, and the products which havebeen subjected to a flame-resistant finish with such flame-resistingagents may cause unexpected difficulties when they are brought intocontact with the skin. In addition, if low molecular weightflame-resisting agents are used in a wet spin' preparation of artificialfibers or semisyntheti'c fibers, the low molecular weight flameresistantagents will not be held in the filaments, but will tend to flow out ofthe filaments into the coagulation bath as the filaments are beingregenerated from the coagulation bath. Consequently, alarge quantity ofthe flame-resistant agents must be added to the spinning solution, whichtends to contaminate thecoagula tion bath and increase the cost andamount of labor required for cleaning the bath.- 7

A variety of high molecular weight agents have been investigated in aneffort to avoid the defects of the low molecular weight flame-resistantagents. For example,

as disclosed in the specification of Japanese Pat. No. 17088/1967,flame-resistant agents of phosphonate polymers have been publicly knownwhich are obtained by reacting a ketone with a cyclic chlorophosphiteunder mild conditions. However, the phosphoruscontaining polymersdisclosed in that publication have terminal free hydroxyl groups whichrenders the substance weakly acidic so that it tends to react withalkali to impart water solubility. Products treated with suchsubstances, therefore, are not completely washresistant. The presence ofterminal alcoholic or acidic hydroxyl groups suggests that the polymersper se are reactive, and chemical changes can occur during the course ofsuch operations as dyeing, bleaching and scouring of high molecularmaterials, such as fibers and plastics, which can cause variousproblems. Further, phosphine-like substances are inevitably generatedfrom the polymers during these operations, which imparts odor andtoxicity to the finished materials.

It is an object of this invention therefore to eliminate theaforementioned defects of such conventionally known flame-resistantagents.

SUMMARY OF THE DISCLOSURE The process of the present invention isaccomplished by applying a phosphorus-containing compound such as anoligomer or polymer, to combustible materials at a temperature below thedecomposition point thereof, said phosphorus-containing oligomer orpolymer being obtained by reacting a tertiary phosphite (A) of thegeneral formula:

(A) a dialkyl phosphite halogenide (B) of the general formula:

' a cyclic halogenophosphite (C) of the general formula:

wherein R, and R represent alkyl groups having one to four carbon atomswhich may be substituted with chlorine or bromine, X represents chlorineor bromine, R through R represents hydrogen or methyl groups, Rrepresents hydrogen or an alkyl group having one to three carbon atoms,and R and R each represent methyl groups or alkyl groups having a totalof five carbon atoms, or R and R together form a cyclohexane ring.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The standard molar ratioof components (A)(E) in the preparation of this compound is about l:l :ll,0O0:1:l 1,000. Preferably, (D) is used in an excess amount relative to(A) or (B), and (E) is used in an excess amount relative to (C). (D) isused in an amount of ll.7 moles, preferably l-l .3 moles, per mole of(B) or (A), and (E) is used in an amount of 1-1.5 moles, preferably1-1.25 moles per mole of (C).

Suitable tertiary phosphites used in the preparation of these compounds(oligomers and polymers), include trialkyl phosphites such as trimethyl,triethyl, dimethyethyl, tripropyl, triisopropyl and tributyl phosphites,and halogen-containing trialkyl phosphites, such as tris- Z-chloroethyl,tris-2-bromoethyl, tris-2,3- dichloropropyl, tris-2,3-dibromopropyl andtris-2,3- chlorobromopropyl phosphites.

Suitable dialkylphosphite halogenides, include dimethyl, diethyl,methylethyl, dipropyl, diisopropyl and dibutylphosphite halogenides anddihalogenoalkylphosphite halogenides, such as bis-2-chloroethyl, bis-2-bromoethyl, bis-2,3-dichloropropyl, bis-2,3- dibromopropyl andbis-2,3-chlorobromopropylphosphites. Halogen-containing trialkylphosphites and dihalogenoalkyl phosphite halogenides are quiteadvantageous starting materials from an industrial point of view, sincethey can be prepared easily at a low price by reacting phosphorustrichloride or phosphorus tribromide with an epoxide of ethylene oxide,propylene oxide or epihalohydrin in the absence or presence of acatalyst, such as magnesium chloride, aluminum chloride or ferricchloride.

Suitable cyclic halogenophosphites include 2-chlorol,3,2-dioxaphospholan, 2-bromo-l ,3,2-dioxaphospholan,2-chloro-4-methyl-l,3,2,-dioxaphospholan, 2- bromo-4-methyl-l ,3,2-dioxaphopholan, 2chloro-4,5 dimethyl-l ,3,2-dioxaphospholan,2-chloro-4-methyll,3,2-dioxaphospholinan and 2-chloro-4,5-dimethyl-1,3,2-dioxaphospholinan. Those compounds can be prepared easily bereacting an a-glycol or B-glycol with phosphorus trichloride orphosphorus tribromide at a low temperature with the evolution ofhydrogen halide.

Suitable ketones include aliphatic or alicyclic ketones having six orless carbon atoms, such as methylethyl ketone and cyclo-hexanone.

Suitable aldehydes include the aliphatic aldehydes having four or lesscarbon atoms, such as formaldehyde, acetaldehyde, propionaldehyde andbutylaldehyde and halogen-containing aliphatic aldehydes such as chloraland bromal.

Generally, the reaction of a cyclic halogenophosphite and a ketoneproceeds indispensably in the presence of water to form aphosphorus-containing polymer containing a terminal hydroxyl group.However, it has been found that the reaction proceeds smoothly in theabsence of water, if a tertiary phosphite, a dialkyl phosphitehalogenide, and an aldehyde are incorporated in the reaction system, toform a phosphorus-containing polymer having a terminal group stabilizedwith an ester group. The molecular weight of the resulting polymer isreduced as the amounts of the tertiary phosphite,

' dialkyl phosphite halogenide and aldehyde per cyclic halogenophosphiteand ketone are increased. On the other hand, the molecular weight isincreased as the amounts of the tertiary phosphite, dialkyl phosphitehalogenide and aledhyde per cyclic halogenophosphite and ketone aredecreased. The molecular weight therefore can be precisely regulated.

In the preparation of said compounds, a mixture of an aldehyde and aketone is generally added dropwise at a temperature below ambienttemperature, preferably at a temperature of between -l0 C, into amixture of a tertiary phosphite, a dialkyl phosphite halogenide andcyclic halogenophosphite. Alternatively, the mixed phosphorus compoundmay be added dropwise into the aldehyde and ketone mixture. The reactionmay be carried out in general in the absence of a solvent or in thepresence of an inert solvent, such as carbon tetrachloride or ethanedichloride. In those processes in which the product is subjected to asubsequent procedure, as will be further discussed below, it isconvenient to use a solvent having a boiling point which approximatesthe isomerization temperature, such as ethane tetrachloride oro-dichlorobenzene. The reaction of the mixed phosphorous compounds withthe aldehyde and ketone proceeds smoothly in a slightly exothermicmanner during which the reaction mixture becomes gradually more viscousor glassysolid. Thus the resulting phosphorous compound containsphosphorus in the form of pentavalent phosphonate and trivalentphosphite.

It was observed by means of a nuclear magnetic resonance spectrum, thatif the compound of this invention is subjected to thermal isomerization,the trivalent phosphorus is completely converted into a pentavalentphosphonate type. The isomerization is performed at a temperature in therange of l00200 C, preferably l40-170 C for from 30 minutes to 10 hours,preferably 2-3 hours. A slight, but not vigorous, heat generation isobserved. The isomerization may be performed either in the absence of asolvent or in the presence of a solvent having an adequate boiling pointas above, such as ethane tetrachloride or o-dichlorobenzene. Inertsolvents suitably used in the isomerization include, in addition to theabove compounds, cumene, pseudocumene, mineral spirit, xylene,turpentine oil, para-cymene and decalin. A compound having a relativelylow boiling point, such as toluene or trichloroethylene may also be usedtogether with the above solvents in a small amount (about 10-20%). Theproducts may be used either before or after the thermal isomerization inthe present invention.

Although the structure of the phosphorus-containing compound obtained inthe above described manner is not completely understood, it is believedthat it corresponds to the following structure, based on the fact thatno free hydroxyl groups are detected. The terminal groups are stabilizedby an ester group.

wherein n represents an integer of l-l,000, R represents a group of andR through R have the same meanings as above.

The decomposition points 4 of the phosphoruscontaining compoundsmeasured, according to differential thermal analysis, will varydepending upon the molecular weight. In general, the decomposition pointis increased as the molecular weight is increased; [I] being around 200C and [II] being around 200-250 C. The phosphorus-containing compoundsare preferably applied to combustible materials at a temperature belowtheir decomposition points.

Various materials can be finished according to the process of thepresent invention including fibers, synthetic resins and various rawmaterials. For instance, treatable fibers include natural fibers, suchas cotton, silk, wool and hemp; artificial fibers, such as filamentsmade according to viscose method or cuprammonium process; staple fiberand cellulose acetate; and synthetic fibers, such as polyamides,polyolefins, polyesters, polyacrylics and vinylon, and mixed yarns andblended fabrics thereof; Synthetic resins include polyolefins,polystyrenes, polyethers, polyamides, polyacrylics, epoxides, alkyds,polyurethanes, polyvinyl chloride and cellulose esters. They may be inthe form of molded compositions, extruded compositions, films, sheets,and surface-constructing compositions, coating compositions, foams andrubbery compositions. Further, not only the finished artificial orsynthetic fibers can be treated according to this invention, but alsospinning solutions (dope) or emulsions can be treated as well. As forcoating compositions, the original solutions thereof may be also deemedas substrates. in addition, printing papers, packing-papers, cardboards,woods, compressed plates and saw-dust may be included. The combustiblematerials of the present invention are intended to include all of theabove materials. There is no strict limitation on the quantity ofphosphorus-containing compounds which can be suitably used in carryingout the process of the present invention. They are effective, however,in amounts of at least 1-2% by weight (solid standard) based oncombustible materials, with the maximum amount being above 50% byweight.

The phosphorus-containing compound may be applied to the above variouscombustible materials by spraying, impregnation, coating or mixing. Thephosphorus-containing compounds of the present invention are in the formof viscous liquids or glassy-solids depending upon the particularmolecular weight. They are all soluble in low aliphatic alcohols, suchas methanol and ethanol, acetone, methylethyl ketone; and halogenatedhydrocarbons, such as ethane dichloride and trichlene. Thus thephosphorus-containing compounds of the present invention withoutdilution, or in a suitably diluted form, can be applied to natural,artificial or synthetic fibers by spraying or immersion to obtainflame-resistant finished products which have good wash and dry cleaningresistance.

If the phosphorus-containing compounds of the present invention arediluted with a suitable solvent and vigorously stirred together with anactivating agent with a homomixer or homogenizer, stable emulsions areobtained. impregnation of fibers with the emulsions constitutes anadvantageous finishing method. in dry and wet spinning processes,lasting flame-resistant fibers having excellent physical properties canbe obtained by adding a phosphorus-containing compound of the presentinvention, without-dilution or in a diluted form, with a suitablesolvent dope or spinning emulsion to obtain a dispersion or solution ofthe phosphoruscontaining compound. The dispersion or emulsion is thensubjected to a spinning operation. The phosphorus-containing compoundscan be applied directly to general synehetic resins or can be mixed withthe resins. They are characterized by good compatibility with manypolymeric materials and are capable of imparting excellent flameresistance, plasticization and transparency to these materials. Theyalso have some effect in enhancing the shrinkage and dimensionalstability of the polymeric materials during molding.

Fibers treated with the phosphorus-containing compounds of the presentinvention are stable against almost all types of conventionalafter-treatments to which fibers and fabrics are usually subjected, suchas water washing, bleaching, scouring, dyeing, softening, resintreatment and curing, and the use of the materials of this inventiondoes not require any special procedures. Their use does not result inany deleterious contamination of the scouring bath owing to scatteringor to reattachment of scattered substance to cloth.

No special temperature limitations are required in carrying out theprocess of the present invention. The phosphorus-containing compounds ofthe present invention are quite stable and are characterized bydecomposition points of generally above 200 C. The compounds can be usedat temperatures ranging from ambient temperature up to the temperatureof decomposition. However, it is to be noted that when thephosphorus-containing compounds of the present invention are used in theform of a solvent solution, the use temperature should be below theboiling point of the solvent.

There are no special procedural requirements as far as the particularquantity of phosphorus-containing compound used. The desirable effectsare generally obtainable by using the compounds in an amount of at leastabout l2% by weight (solid standard) based on combustible materials, themaximum amount being about 50% by weight.

The materials of the present invention can be used in combination withan amino resin, a phenolic resin, an epoxy resin, etc., depending uponthe particular finishing requirements. The materials and technique ofthe present invention provide the following advantageouscharacteristics:

1. The flame-resistant effects are stable against water washing and drycleaning.

2. The toxicity is very low.

3. The products are odorless.

4. The finished products have good stability to sunlight and no colorchange is observed.

5. The dyeability of the materials being finished is not adverselyaffected.

The process of the present invention will be illus trated below withreference to the following Examples which are provided herein forpurposes of illustration only.

In those Examples, parts and percentages are given by weight.

REFERENCE EXAMPLE 1 Preparation of phosphorus-containing compounds 1 and2:

In a four-necked flask provided with thermometer, stirrer, condenser anddropping funnel, tris (2- chloroethyl) phosphite, bis(2-chloroethyl)phosphochloridite and 2-chloro-4-methyl-l,3,2-dioxaphospholan werecharged in amounts listed in Table 1. At a temperature below 10 C whilestirring, a mixture of acetaldehyde and acetone in amounts listed inTable 1 was added dropwise therein. After completion of the addition,the mixture was allowed to stand while stirring for 2 hours or overnightand then heated to 50-80 C under a reduced pressure of -10 mm Hg toremove volatile components. Yields and molecular weights of theresulting phosphorus-containing polymers of phosphonate-phosphite typeare shown in Table l.

TABLE 1 Compounds numbers Reaction components and results 1 2Tris(2-chloroethyl) phosphite, [1. (molar ratio) 40 (1) 27 (1)Bis(2hloroethyl) phosphorochlorldite, g. (molar ratio) 34 (1) 23 (l)2-chloro-4-methyl-1,3,2-dloxaphospholan, g.

(molar ratio) 84 (4) 84 (6) Acetaldehyde, g. (molar ratio) (1.53) 1(1.56) Acetone, g. (molar ratio). 44 (5) 44 (7.5) Yield (afterconcentration under reduced pressure), g 188 175 Molecular weight (afterconcentration under reduced pressure) 1, 260 1,680 d c {1 percent 14. 815.0

m Cl, percent 21.3 21. 5

NO'llL-JtlOlul' ratio is based on trls(2-chloroetliyl) phosphitc as l.

REFERENCE EXAMPLE 2 Preparation of phosphorous compounds 3 to 5:

The reaction components listed in Table 2 were reacted in the samemanner as in Reference Example 1. After concentration under reducedpressure, the resulting phosphorus-containing compounds ofphosphonate-phosphite type, without any treatment, were isomerized atl40l 50 C for 2-3 hours. The products were colorless honey-like orglassy solids. Yields and molecular weights are shown in Table 2.

i TABLE 2 Compounds numbers Reaction components and results 3 4 5Trls(2-chloroethyl') phosphite, g.

(molar ratio) 121 (1) 81 (l) 59 (1) Bis(2-chloroethyl)phosphorochloridite, g. (molar ratio) 101 (1) 68 (1) 5O (1)2-chlor0-4-methyl-1,3,2-dioxaphospholan, g. (molar ratio) 2,086 (33)2,028 (48) 2, 163 (70) Acetaldehyde, g. (molar ratio) 31 (1.56) 21(1.56) (1. 54) Acetone, g. (molar ratio) 1,075 (41. 2) 1,045 (60) 1,115(87) Yield (after isomerlzation under heating), g 2, 980 3,080 3. 100Molecular weight (after lsomerizatlon under heating) ..L (SigOg 9,1203 mgop perccn 1 "icl, percent 22. 0 22. 5 21. a

Norr:.-Molar ratio is based on trls(2-chloroethyl) phosphlte as 1.

REFERENCE EXAMPLE 3 TABLE 3 Compounds numbers Reaction components andresults 6 7 Tris(2-bromoethyl) phosphite, g. (molar ratio)" 81 (l) 81(1) Bis(2-bromoethyl) phosphorobromidide, g.

(molar ratio) 72 (1) 72 (1) 2-bromo-4methyl-1,3,2-dioxaphospholan,

(molar ratio) 1,850 (50) 2, 959 (80) Acetaldehyde, g. (molar ratio) 14(l. 14 (1. 56) Acetone, g. (molar ratio). 726 (625) 1,161 (100) Yield(after isomerization under heating), g 2, 5 3, 950 Molecular weight(aiter isomerization under heating) P t l3ig0g 213.30g

, percen Product "{Br, percent" 35. 0 34. 2

No'rE.Molar ratio is based on tris(2-bromoethyl) phosphite as 1.

EXAMPLE l A filter paper of l00% cellulose pulp of 173 g/m wasimpregnated with a solution prepared by mixing 10 parts of compound (3)in Reference Example 2, l6.7 parts of 60% resol-type phenolic resinsoluble in methanol and 73.3 parts of methanol, squeezed uniformly witha roll to pickup 200 percent, dried at C for 5 minutes, subjected toheat treatment at 120 C for 3 minutes and finally hardened at 150 C for15 minutes. The paper thus finished had a carbonized area of 25 cm inthe flame-proof test according to 118 Z-2 150 and the times forlingering of flame and embers were both zero. The rupture strength ofthe finished paper was 1.8 Kg/cm (the strength of paper not containingcompound 3 was l.5 Kg/cm and that of unfinished base paper was 0.4 Kg/cmThere was not observed odor, remarkable coloring or stickiness.Substantial reduction in flame-resistant effect or tear strength was notrecognized after the finished paper was immersed in water at ambienttemperature for hours and dried.

EXAMPLE 2 A plain weave curtain fabric of spun rayon having a weight of210 g/m was impregnated with solution prepared by dissolving 20 parts ofcompound (5) in Reference Example 2, 1.5 parts ofmethylhydrodienepolysiloxane having degree of polymerization of 50 and0.5 part of zinc octenoate in 78 parts of trichloroethylene. The fabricwas squeezed with an iron roll to pickup 100 percent, air-dried at 80 Cfor 5 minutes and subjected to heat treatment at C for 5 minutes. Thefabric thus finished had a carbonized area of 30 cm. The lingering offlame and embers times were both zero in the flame-proof test accordingto H8 Z2 1 50. The finished fabric was soft. Water-repellency accordingto AATCC spray test was 100. As for flame-resistant effect after washingthree times according'to JlS L-l042 F-l, the carbonized area was 33 cmand the times for lingering of flame and embers were both zero.

EXAMPLE 3 in 40 parts of compound (1) in Reference Example 1, 3.5 partsof polyoxyethylene nonylphenol ether having 60 moles of ethylene oxideadded and 2.5 parts of polyoxyethylene nonylphenol ether phosphoricester were added. The mixture was then added with 54 parts of waterdropwise while stirring to obtain an emulsion, which was treated withEppenbach homogenizer to obtain stable emulsified dispersion havingaverage particle diameter of l-l.5 microns. 40 parts of the emulsifieddispersion thus obtained was diluted with 60 parts of water and sprayedon a wallpaper of viscose straw yarn lined with paper with a spray gunat the ratio of 100 g/m The wallpaper was dried at 80 C for 5 minutes.When a match was allowed to come near the surface of the wallpaperapplied to wall, no flame spread was observed but carbonization of areacontacted with flame.

EXAMPLE 4 On a parting paper applied with silicone resin, mixture of 15parts of the emulsified dispersion of Example 3, 85 parts of 45% aqueousdispersion of emulsion copolymer of ethyl acrylate, acrylonitrile,acrylic acid and acrylamide in the ratio of 88:6:3:3 (by weight), 5parts of methylated methylolmelamine and 0.5 part of an organic aminehydrochloride was cast. After drying and heat treatment, the resultingfilm was transparent and noncombustible. The mixture was quite useful asadhesive for noncombustible non-wovenfabric, flocky finished cloth andlined cloth. e

EXAMPLE 15 parts of a copolyiner obtained by pearl polymerization havingcomposition of 84 parts of ethyl acrylate, 15 parts of acrylonitrile and1 part of fl-hydroxyethyl methacrylate, 15 parts of compound (6) inReference Example 3 and 70 parts of toluol were mixed together to obtainhomogeneous viscous solution having viscosity according to Broodfieldviscosimeter of 19,000 centipoises. In 90 parts of the solution, partsof antimony trioxide were added and the mixture was stirred to obtain ahomogeneous paste. The paste was then mixed with 1 part of butylatedmethylolmelamine. Both faces of a vinylon-cotton canvas were coated withthe pasty mixture in the amount of 120 g/m and air-dried at 100 C. In aflame-proof test according to a vertical test method of AATCC, the thusfinished canvas had a carbonized distance of 10 cm and the times forlingering of flame and embers were both zero. The flameproof propertywas stable against water. No odor or remarkable hardening in handlingwas observed in the finished canvas. It was particularly suitable fortent or sheets to be used in transportation.

EXAMPLE 6 EXAMPLE 8 EXAMPLE 9 Compound (2) in Reference Example 1 wasadded to a viscose having a cellulose concentration of 8% at the ratioof cellulosezcompound (2) 100:20. Spinning and finishing were carriedout in the same manner as in Example 7.

The test results of the product are shown in Table 4.

EXAMPLE 10 Spinning and finishing were carried out in the same manner asin Example 9 except that parts of compound (6) in Reference Example 3were used instead of 20 parts of compound (2) per 100 parts ofcellulose. The test results of the product are shown in Table 4.

EXAMPLE 1 l Spinning and finishing were carried out in the same manneras in Example 10 except that parts, not 30 parts, of compound (6) wereused. The test results are 2.5 parts of compound (5) in ReferenceExample 2, 30 shown in Table 4.

TABLE 4 Time for Dr Carbonilingering Time for Dry elonga NOtlUlill Itemsration of flame embers strength tion strength Examples: (percent)(second) (second) (g./d.) (percent) (Ln/d 7 85 0 0 2.71 20.0 1.50 79 0 0Z. 77 20. 3 1. 60 62 0 0 2. 87 20. 5 l. 64 89 0 0 2.49 20.5 1.60 92 0 02.41 21.4 1.66 Common rayon 2 150 195 2. 80 18. 1 1. 60

Nora-1.Porportion by weight of remaining carbonized part after heatingfrom ambient temperature to 500 C. in a microtltermobalance device fordifferential thermal analysis was taken as earbonization percentage.

NOTE 2,-2.5 mm. butane gas flame was brought in contact with a bundle offilament and times for lingering oi flame and time for embers afterremoval of the flame were measured.

25 parts of cellulose acetate (degree of acetylation:52%) and 72.5 partsof acetone were mixed to obtain a homogeneous solution, which was thenspun under a spinning pressure of 20 Kg/cm at 120 denier (32 filaments),oil-twisted in the usual manner and reeled. The resulting celluloseacetate filament was woven into a cloth. After scouring, the cloth wasshown to be noninflammable. Only portions brought into contact with theflame were observed'to melt. There was observed neither odor norirritation. The cloth did not undergo any significant color change inexposure to sunlight and did not lose its flameproof property byrepeated domestic washing.

EXAMPLE 7 Emulsified dispersion obtained by mixing 100 parts of compound(5) in Reference Example 2 with 6 parts of polyoxyethylene nonylphenolether emulsifier and 44 parts of water was added to viscose having acellulose concentration of 8% at the ratio of cellulose: compound (5)100:20. The mixture was spun into a Mullers bath and scoured and driedin a usual manner.

The results of test of the product areshown in Table 4.

EXAMPLE 12 95 parts of polystyrol having an average degree ofpolymerization of about 1,000 and an average particle diameter of 0.6mm, obtained by bulk polymerization in batch were blended and kneadedwith 5 parts of compound (3) in Reference Example 2 and the mixture washeated to melt and subjected to injection molding. Temperature of theinjection molding cylinder was 220 C and the injection pressure wasabout 900 Kglcm For comparison, the similar finishing was effectedwithout using compound (3). Figures in parentheses are for the caseswherein compound (3) was not used in the following descriptions.Rockwell hardness of the molded good was M- (M-), tensile strengthaccording to the description of ASTM D'63 8-5 8T was 431.3 Kg/cm (509.5Kg/cm) and tensile elongation was 1.3% (1.8%). Degree of cloudiness ofthe molded good caused by the incorporation of the compound according tothe description of ASTM D-572-50 was 10, and index of refraction was n1.50 (1.59). Degree of hygroscopicity according to the description ofASTM D-570-42 during 24 hours was 0.002% (0.001%). Coloration afterirradiation with a Fade- Ometer for 300 hours was negligible. If themolded good containing said compound placed on a wirenetting was heatedto set fire from below, the molded good melted but did not burn up,while the molded good not containing said compound burned in a flame andmelted.

EXAMPLE l3 10 parts of compound (5) in Reference Example 2 were mixedwith parts of tricresyl phosphate to obtain a homogeneous solution. 20parts of the mixture was mixed with 100 parts of 50% emulsion ofpolyvinyl acetate (viscosity 15,000 cps., containing 7% of polyvinylalcohol as protective colloid but no plasticizer) to obtain ahomogeneous solution. Dry film prepared from the mixture was carbonizedbut did not burn when it was brought into contact with a flame. The filmwas flexible and had good transparency and properties suitable foradhesive for flame-proofing wallpapers and printing binders. The filmprepared from said mixture was resistant to sunlight and was excellentas a flameresistant painting resin.

EXAMPLE l4 4 parts of compound (6) in Reference Example 3 were added ina mixture of 100 parts of 35% solution of linear polyester urethanepolymer having reactive OH group at the terminal in ethyl acetate (tradename: Crisvon N-183, a product of Dainihon Ink Kagaku Kogyo Co., Ltd.and 6 parts of polyfunctional polyisocyanate cross-linking agent (tradename: Crisvon N- 189) and 6 parts of an accelerator for urethanationreaction (trade name: Crisvon Accel, a product of Dainihon Ink KagakuKogyo Co., Ltd.) and the whole was mixed homogeneously. A silicone paperwas applied with the mixture and dried at 120 C for 5 minutes to obtaina film having a thickness of 0.25 mm. For comparison a similar treatmentwas effected without using said compound. Figures in parentheses givenbelow are for the cases wherein said compound was not used. Tensilestrength of the film was 340 Kg/cm (355 Kglcm and elongation was 740%(730%). The film obtained according to the process of the presentinvention had excellent transparency and softness and very slightstickiness. If the film finished according to the process of the presentinvention was brought into contact with a flame, it only melted, but didnot burn, while the film not containing said compound burned. Theflame-proof property of the film of the present invention was not lostby immersion in water.

EXAMPLE Water was added to 30 parts of the emulsified dispersion inExample 3 to make the total weight 100 parts. A roll of curtain lacemade of polyester synthetic filament (polyethylene glycol terephthalate)dyed in black was immersed in the mixture, squeezed to pickup 100% andheat-treated at 130 C for 3 minutes. The roll thus finished gaveresults'of seven times in flame-contact test effected according tocombustion test (coil method) described in the Official Gazette (ExtraEdition No. 22) published on Mar. 28, 1969, while nonfinished roll gavethe results of two times. The finished clo'th was then subjected towashing three times wherein the cloth was washed in a domestic electricwashing machine with 0.2% soap solution at 40 C for minutes, rinsed withcold water for 5 minutes and dried. The flame-proof effect of the clothwas not lost after the wash treatment.

EXAMPLE 16 The test for finished material was effected in the samemanner as in Example 15 by using an emulsified dispersion obtained byemulsifying 40 parts of oligomer mixture composed of 50% of compound (6)in Reference Example 3 and 50% of compound (2) in Reference Example I inthe same manner as in Example 3. Flame-proof effect and resistance towash stood comparison with those of Example 15. As for handling of thefinished roll, stickiness was low as compared with that of Example 15.

EXAMPLE 17 A mixture of parts of compound (6) in Reference Example 3 and30 parts of tricresyl phosphate was emulsified under the same conditionsas in Example 3 to obtain stable emulsified dispersion. The emulsifieddispersion was subjected to a finishing test in the same manner as inExample 15. Flame-proof effect of the finished cloth stood comparisonwith that of Example 15. The hand of the finished cloth was not stickyand was as pleasing as in Example 16.

EXAMPLE l8 In parts of unsaturated polyester resin (trade name: Polylite8007, a product of Dainihon Ink Kagaku Kogyo Co., Ltd.), 10 parts ofcompound (7) in Reference Example 3 and 1 part of 55% solution ofmethylethyl ketone peroxide in dimethylphthalate were added. Squareplates of side of 30 cm having thickness of 3 mm were mblded at about 40C, allowed to stand for 30 minutes, cured at about 60 C for 8 hours andfinally cured at lO0-l 10C for about 2 hours. Flameproof tests wereeffected according to the description of JIS A-l322. After heating for30 seconds, 1 minute, 2 minutes and 3 minutes, the time for lingering offlame was zero. The flame was extinguished directly after removal fromthe burner. In any period of heating, the flame length was less than 15cm.

EXAMPLE 19 A roll of scoured and bleached cotton poplin weighing l53g/mwas impregnated with a solution of 50 parts of emulsified dispersionof Example 16 diluted with 50 parts of water, squeezedwith a roll topickup 80 percent and dried in hot air at C for 5 minutes. The resultsare shown in Table 5.

EXAMPLE 20 Cotton fabric the same as that in Example 19 was immersed insolution'prepared by adding in 50 parts of emulsified dispersion inExample 16, 8 parts of reactive wrinkle-proof agent ofdimethylolethylene urea cellulose, 2 parts of 80% aqueous solution ofmethyletherified trimethylol mealmine, 2 parts of acid catalyst of anorganic amine hydrochloride (trade name: Catalyst 376, a product ofDainihon Ink Kagaku Kogyo Co., Ltd.) and 38 parts of water. The fabricwas then squeezed to pickup 80 percent with a roll, dried at 90 C for 5minutes and heat-treated at C for 5 minutes.

The results are shown in Table 5.

EXAMPLE 21 Test was effected under the same conditions as in Example 20except that 10 parts of water was reduced from the treating solution and10 parts of flameresisting agent of methylol compound ofdimethylphosphonopropionamide were added instead. The results are shownin Table 5.

:l-l ,500 and carrying out the reaction at a temperature of from to C.

2. A process for preparing a trivalent phosphorus- TABLE 5 Flame-prooftest according to JIS Z-2l50 Wrinkle Tear resist ance, strength,

Time for Carbonized Carbonized l0ngilongilingering Time for area afterarea after tudinal tudinal Carbonized of flame embers the first thethird direction direction Item area (cm?) (second) (second) wash (em?)Wash (0111. (percent) (g.)

Example:

Poplin not treated. 1 0 39 960 1 Entirely destroyed.

Nora 1.Conditions for wash were according to JIS 11-1041.

NOTE 2.-Degree of wrinkle resistance was measured according to J IS.

NOTE 3.Tear strength was measured according to tear test of J IS.

Having now fully described the invention, it will be apparent to one ofordinary skill in the art that many changes and modifications can bemade thereto without departing from the spirit or scope thereof.Accordingly,

What is intended to be covered by letters patent is: l. A process forpreparing a trivalent phosphoruscontaining compound characterized bygood flameresistant properties which comprises the reaction product of atertiary phosphite of the general formula wherein R and R, represent analkyl group having one to four carbon atoms which may be substitutedwith chlorine or bromine, X represents chlorine or bromine, R through R,represent hydrogen or methyl, R represents hydrogen or an alkyl grouphaving one to three carbon atoms, and R, and R represent alkyl groupshaving a total of two to five carbon atoms or R and R together form acyclohexane ring, wherein said reaction product is obtained by adding amixture of said aldehyde (D) and said ketone (E) to a mixture of atertiary phsophite (A), a dialkyl phosphite halogenide (B) and a cyclichalogenophosphite (C) in a molar ratio of (A):(B):(C):(D):(E):1:l:1-l,000:l1:7-

containing compound characterized by good flameresistant propertieswhich comprises the reaction product of a tertiary phosphite of thegeneral formula (A) a dialkylphosphite halogenide of the general formula(B) a cyclic halogenophosphite of the general formula R5 Ra-CHO\ /(IJHOP-X or Rt-cH \P-X R4CH0 CHO/ I I: (C)

an aldehyde of the general formula R Cl-lO and a ketone of the generalformula wherein R and R represent an alkyl group having one to fourcarbon atoms which may be substituted with chlorine or bromine, Xrepresents chlorine or bromine, R through R represent hydrogen ormethyl, R represents hydrogen or an alkyl group having one to threecarbon atoms, and R and R represent alkyl groups having a total of twoto five carbon atoms or R and R together form a cyclohexane ring,wherein said reaction product is obtained by reacting (A), (B), (C), (D)and (E) in a molar ratio of l:l:l-l,000:l-l:7- :ll,500 at a temperatureof from 0 to 10 C., while stirring for a period of from 2 hours toovernight, then heating to a temperature in the range of from 50 to C.under a reduced pressure in the range of from 5 to 10 mmHg for a periodsufficient to remove volatile compounds.

' UNITED STATES PATENT OFF ICE CERTIFICATE OF CORRECTION,

Patent:v No. 3 760 Dated September r 73 Inventor) MASAO YOSHIZAWA ET ALIt; is certified thet error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 3 line 55, delete -"aledhyde" and inserr therefor al dehyde-Column 13 l ine 64, delete "1:7" and insert therefor! -1 .7-

Column 14; line delete "(1C)" and insert therefor -'0 T Column 14,1ine'5 6, delete '1:7" end insert therefor;-..- 1.7--.

Signed and sealed this Pith-day or September 197 (SEAL) Attest: v I ImccoY GIBSON, JR MARSHALLDANN Attesting Officer Commissioner of PatentsuscoM M-nc scan-P09 R INTING OFFICE 1 15.9 O366-334 k ".5. GOVERNMENT? FORM PO-1050 (10-69)

2. A process for preparing a trivalent phosphorus-containing compoundcharacterized by good flame-resistant properties which comprises thereaction product of a tertiary phosphite of the general formula (R1O)3P,(A) a dialkylphosphite halogenide of the general formula (R2O)2PX, (B) acyclic halogenophosphite of the general formula